U.S. patent application number 10/406856 was filed with the patent office on 2004-10-07 for glycine-free antiperspirant salts with betaine for enhanced cosmetic products.
Invention is credited to Cai, Heng, Holerca, Marian, Tang, Xiaozhong.
Application Number | 20040198998 10/406856 |
Document ID | / |
Family ID | 33097405 |
Filed Date | 2004-10-07 |
United States Patent
Application |
20040198998 |
Kind Code |
A1 |
Holerca, Marian ; et
al. |
October 7, 2004 |
Glycine-free antiperspirant salts with betaine for enhanced
cosmetic products
Abstract
A glycine-free aluminum and/or zirconium Betaine salt having a
metal to chloride molar ratio in the range of 0.3-2.5:1, a
Betaine:aluminum molar ratio in the range of 0.05-1.0:1 and/or a
Betaine:zirconium molar ratio in the range of 0.2-3.0:1, wherein
the Betaine has the following Formula I: 1
Inventors: |
Holerca, Marian; (Highland
Park, NJ) ; Tang, Xiaozhong; (Bridgewater, NJ)
; Cai, Heng; (Yardley, PA) |
Correspondence
Address: |
Colgate-Palmolive Company
909 River Road
P.O. Box 1343
Piscataway
NJ
08855-1343
US
|
Family ID: |
33097405 |
Appl. No.: |
10/406856 |
Filed: |
April 4, 2003 |
Current U.S.
Class: |
556/56 ;
556/181 |
Current CPC
Class: |
A61K 8/26 20130101; A61K
8/44 20130101; A61K 8/28 20130101; A61Q 15/00 20130101; C07F 7/003
20130101; C07F 5/069 20130101 |
Class at
Publication: |
556/056 ;
556/181 |
International
Class: |
C07F 007/28; C07F
005/06 |
Claims
We claim:
1. A glycine-free aluminum and/or zirconium Betaine salt having a
metal to chloride molar ratio in the range of 0.3-2.5:1, a
Betaine:aluminum molar ratio in the range of 0.05-1.0:1 and/or a
Betaine:zirconium molar ratio in the range of 0.2-3.0:1, wherein
the Betaine has the following Formula I: 4
2. A salt according to claim 1 wherein the metal to chloride molar
ratio is in the range of 0.9-2.1:1.
3. A salt according to claim 1 comprising aluminum and wherein the
Betaine:aluminum molar ratio is in the range of 0.05-0.26:1.
4. A salt according to claim 1 comprising aluminum and wherein the
Betaine:aluminum molar ratio is in the range of 0.05-0.16:1.
5. A salt according to claim 1 comprising zirconium and wherein the
Betaine:zirconium molar ratio is in the range of 0.4-1.5:1.
6. A salt according to claim 3 or claim 4 comprising zirconium and
wherein the Betaine:zirconium molar ratio is in the range of
0.4-1.5:1.
7. An antiperspirant and/or deodorant product made with a salt
according to any one of claims 1, 2, 3, 4 or 5.
8. A stick antiperspirant and/or deodorant comprising: 40-55%
cyclomethicone; 20-30% stearyl alcohol; 7-15% talc; 15-22% of a
salt according to claim 1 added in powder form; and 1-3%
fragrance.
9. A roll-on antiperspirant and/or deodorant comprising: 45-65%
cyclomethicone; 0.1-10% cyclomethicone/dimethicone copolyol; 10-25%
of a salt according to claim 1 in a solution as 25-45% actives on
an anhydrous basis in water; 5-30% water; and 1-3% fragrance.
10. A soft solid antiperspirant and/or deodorant comprising: 40-70%
elastomer in cyclomethicone; 5-15% polyethylene beads having a
density in the range of 0.91-0.98 g/cm.sup.3 and an average
particle size in the range of 5-40 microns; 10-20% C12-15
alkylbenzoate; 0.1-25%% of a salt according to claim 1 added in
powder form; 1-15% dimethicone; and 1-3% fragrance.
11. A gel antiperspirant and/or deodorant comprising: 5-50%
cyclomethicone; 0.1-10% cyclomethicone/dimethicone copolyol; 0-10%
hydrogenated polyisobutene 250; 0-10% C12-15 alkylbenzoate; 0-10%
dimethicone; 0.1-25% of a salt according to claim 1 added in powder
form or as 10-25% of active in solution (25-45% actives on an
anhydrous basis); 5-50%; and 1-3% fragrance.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a class of glycine-free
antiperspirant salts combined with Betaine that may be used to
formulate antiperspirants with enhanced stability and efficacy.
BACKGROUND OF THE INVENTION
[0002] A variety of art is available that describes various salts
and methods of making them.
[0003] U.S. Pat. No. 4,331,609 to Orr teaches an antiperspirant
active comprising aluminum and zirconium made with separate
aluminum and zirconium compounds as well as a neutral amino acid
wherein the molar ratio of neutral amino acid to total metal is
from about 0.90 to about 0.24. The total metal:chlorine ratio in
the complex that is formed is less than 1.30.
[0004] EP publication number 0 047 650 describes aqueous
solution-stable antiperspirant complexes comprising an aluminum
compound, a zirconium or hafnium compound, a water soluble neutral
amino acid and an inorganic acid. The molar ratio of neutral amino
acid to total metal is from about 0.90 to about 0.24 in an aqueous
system, and the molar ratio of neutral amino acid to total metal is
from about 0.90 to about 0.75 in a non-aqueous system. The total
metal:chlorine ratio in the complex that is formed is less than
1.30.
[0005] United Kingdom Patent Application GB 2,076,289 describes an
antiperspirant compositions comprising a combination of an aluminum
chloride and an aluminum zirconium hydroxychloride in a synergistic
mixture. The metal:chloride ratio is less than 0.9.
[0006] Canadian Patent 1,153,313 describes an antiperspirant
composition which contains a buffering agent such as glycine with a
synergistic mixture of aluminum chlorohydrate, aluminum chloride or
aluminum zirconium polychlorohydrate complex. The molar ratio of
aluminum to chloride is in the range of 0.78:1 to abut 1.95:1.
Various salts are described which have a metal:halide ratio of
2.1:1-0.9:1. The glycine:zirconium ratio is much less than 1:1.
[0007] U.S. Pat. No. 4,871,525 to Giovanniello et al describes a
solid powder of aluminum zirconium hydroxyl halide glycinate
complex having improved antiperspirant activity wherein the glycine
is used to prevent gel formation. The ratio of Zr to glycine is
less than 1:1.
[0008] U.S. Pat. No. 6,126,928 to Swaile describes antiperspirant
compositions wherein the molar ratio of neutral amino acid to total
metal (aluminum+zirconium) is from about 0.90 to about 0.24, and
the mole ratio of (aluminum+zirconium):chlorine is less than about
1.30:1.
[0009] U.S. Pat. No. 6,066,314 to Tang describes the use of post
added glycine to aluminum zirconium salts in an amount in the range
of 1:1.2-1:5 of zirconium:amino acid on a weight:weight basis.
[0010] None of the above cases described the combination of metal
to chloride in combination with the Betaine (as defined herein) to
zirconium ratio as found in the instant invention. Thus, it is
surprising that the antiperspirant actives described in this
invention provide more efficacious cosmetic products.
[0011] The term "betaine" is used in a variety of ways. In
particular, a variety of uses of betaines with long chains can be
found in the surfactant art. Such betaines may be represented by
the following Formula A where n>0: 2
[0012] The methyl groups can be replaced with other longer chain
alkyls and can be straight chain or branched.
[0013] The Betaine (defined below) of this invention, however, is
not a surfactant and has been found to have properties important to
the field of antiperspirant salts that contain zirconium. The
Betaine used in this invention is a natural product found in a
number of plants in the Chenopodiaceae family, and also in fish and
selected legumes. Extracted most often from sugar beets (Beta
Vulgaris), it is reported as an extremely versatile molecule with a
wide range of applications: food supplement, anti-irritant, skin
moisturizer, skin-softening agent, skin-conditioning agent,
promoter of wound healing and component in cosmetic compositions
for skin aging and stressed skin.
[0014] Betaine in IUPAC nomenclature is
1-carboxy-N,N,N-trimethylmethanami- nium hydroxide-inner salt, with
alternative names including carboxymethyl-trimethylammonium betaine
or (carboxymethyl)trimethylammoni- um hydroxide-inner salt or
glycine betaine or glycoll betaine or glycyl betaine or trimethyl
glycine or trimethylglycoll. For convenience here the material of
Formula I (C.sub.5H.sub.11NO.sub.2; Mass=117.08 amu; molecular
weight=117.15; analysis as C: 51.26; H: 9.46; N: 11.96; O: 27.32)
will be referred to as Betaine. 3
[0015] Betaine appears in numerous patents, with a wide range of
applications. Note that for purposes of this application, the term
"betaine" will be used if any compound of Formula A is described.
The term "Betaine" will be used if only a compound of Formula I is
described.
[0016] PCT Publication WO 00/67726 describes host-guest processes
and formulations containing Betaine for delivering bio-affecting
compounds and topical compositions for cosmetic or pharmaceutical
uses formed by the processes. The processes comprise mixing, in any
order: (i) a nonionic surfactant; (ii) an amphoteric surfactant;
(iii) a solvent for the amphoteric surfactant; (iv) an aromatic
compound; (v) an aluminum cation; (vi) a Lewis acid that is not a
Bronsted-Lowry acid; and (vii) a Bronsted-Lowry acid.
[0017] U.S. Pat. No. 5,877,143 describes a composition containing a
lamellar liquid crystalline phase which comprises betaines and
amine oxides. This is a pumpable, fluid composition of amine oxide,
betaine and/or sultaine is prepared with active concentration of
about 36-45% of these materials by the addition of alkaline earth
or aluminum salts.
[0018] German Patent DE 19725087 is related to cosmetic and
dermatologic oil-in-water emulsion formulations for light
protection containing hydrophobic inorganic micropigments and
hydrophilic surfactants.
[0019] PCT Publication WO 97/23594 describes skin cleansing
compositions with enhanced antimicrobial activity comprising
0.1-30% of an amphoteric, zwitterionic, nonionic, anionic and/or
cationic emulsifier, 0.00001-5% of a Ag compound (AgCl,
Ag.sub.2CO.sub.3, etc.), deposited on a particulate inert support
material (metal oxides, especially TiO.sub.2) as antimicrobial
agent, and H.sub.2O. A typical composition contains cetyl
betaine.
[0020] Japanese Patent JP 52093633 describes chemical polishing
solutions for aluminum and its alloys. Al or its alloys are
chemically polished in a H.sub.3PO.sub.4--H.sub.2SO.sub.4 solution
containing a betaine and organic polythio sulfonic acid salt.
[0021] British Patent GB 2354771 relates to bactericide
combinations in detergents. The detergent comprises a bactericide
in combination with an anionic, cationic, nonionic or amphoteric
surfactant which has a C12-18 alkyl group as the longest chain
attached to the hydrophilic moiety.
[0022] Japanese Patent JP 2001163752 describes long-lasting
cosmetic makeup compositions comprising plate-type glossy polymer
powders and antiperspirants.
[0023] European Patent EP 1005853 describes the use of betaines as
antiperspirants. Mono-, di-, and trimethylammonio-substituted
carboxylic acids (R.sup.1)
(R.sup.2)(R.sup.3)N.sup.+--(CH.sub.2).sub.nC(O)O-- (with
R.sup.1--R.sup.3.dbd.H, Me; n=1-10) are active as antiperspirants
and are compatible with the skin and with other conventional
constituents of antiperspirant and deodorant compositions.
[0024] European Patent EP 1005852 describes the use of functionally
substituted betaines as antiperspirants. Mono-, di-, and
trimethylammonio-substituted carboxylic acids
R.sup.1R.sup.2R.sup.3N+(CH.- sub.2).sub.nCHX(CH.sub.2).sub.mC(O)O--
and/or X(CH.sub.2).sub.nCH(N+R.sup.-
1R.sup.2R.sup.3)(CH.sub.2).sub.mC(O)O-- (R.sup.1--R.sup.3.dbd.H,
Me; m, n=1-8) are active as antiperspirants and are compatible with
the skin and with other conventional constituents of antiperspirant
and deodorant compositions.
[0025] Japanese Patent JP 11130652 discloses skin-conditioning and
moisturizing cosmetics containing clay minerals and
low-molecular-weight betaines to inhibit the release of
pyrrolidonecarboxylic acid (a natural moisturizing factor) from
human skin.
[0026] German Patent DE 2610225 describes aluminum salts of Betaine
chloride being useful as ulcer inhibitors, for treatment of
gastritis, to promote wound healing, and as antiperspirants and
deodorants.
[0027] PCT Publication WO 01/62222 describes cosmetic compositions
containing phospholipids and quaternary amines. The invention
relates to a cosmetic composition, especially for use on aging
and/or stressed skin, the composition comprising, in addition to
water, at least one substance that forms lamellar structures with
water. Compositions including Betaine are described.
[0028] PCT Publication WO 01/47479 assigned to the same owner as
this case describes cosmetic moisturizing compositions containing
quaternary ammonium compounds. Compositions with cocamidopropyl
betaine are described.
[0029] PCT Publication WO 01/39730 describes a cosmetic composition
containing peat and Betaine.
[0030] PCT Publication WO 97/46246 is related to complex
preparations for topical use containing Betaine to stimulate
cellular and physiological processes.
[0031] PCT Publication WO 91/18588 presents a method of reducing
the irritating properties of a cosmetic composition by addition of
Betaine derivatives.
[0032] Japanese Patent JP 03033266 describes modified fabrics
coated with a mixture of dodecyl betaine and other ingredients for
controlling pH change in skin during sweating.
BRIEF SUMMARY OF THE INVENTION
[0033] This invention comprises aluminum and/or zirconium salts
with Betaine as a complexing agent and buffering agent and which do
not contain glycine.
DETAILED DESCRIPTION OF THE INVENTION
[0034] This invention comprises glycine-free aluminum and/or
zirconium Betaine salts having a metal to chloride molar ratio in
the range of 0.3-2.5:1 (especially in the range of 0.9-2.1:1), a
Betaine:aluminum molar ratio in the range of 0.05-1.0:1
(particularly 0.05-0.26:1 and, more particularly, 0.05-0.16:1)
and/or a Betaine:zirconium molar ratio in the range of 0.2-3.0:1
(particularly 0.4-1.5:1).
[0035] The salts of this invention may be made in a variety of
ways:
[0036] Method A: An aluminum chlorohydrate (ACH) solution of ACH
salt in water of suitable concentration is mixed with an aqueous
solution of zirconyl chloride (ZrOCl.sub.2) (or alternatively
combining ZrOCO.sub.3 and HCl to make the zirconyl chloride in
situ) of suitable concentration and powdered Betaine. The mixture
is stirred at room temperature to obtain the salt, or dried to
remove water to come out with powder form of the salt.
[0037] Method B: A suitable commercially available glycine-free
aluminum zirconium tetrachlorohydrex salt, aluminum zirconium
trichlorohydrex, aluminum zirconium pentachlorohydrex, or aluminum
zirconium octachlorohydrex is dissolved in water or water solutions
of glycols and mixed with a sufficient amount of powdered Betaine.
The mixture is stirred at room temperature to obtain the salt, or
the solution is dried to remove water to have a powder form of the
salt. When Method B is used, a suitable salt to use as a starting
material includes various types salts such as aluminum zirconium
chlorohydrex, aluminum zirconium chlorohydrex propylene glycol
complex, aluminum zirconium chlorohydrex dipropylene glycol
complex, and mixtures of any of the foregoing.
[0038] Method C: An aqueous aluminum chlorohydrate (ACH) solution
made from an activated ACH salt of suitable concentration is mixed
with an aqueous solution of zirconyl chloride (ZrOCl.sub.2) (or
alternatively combining ZrOCO.sub.3 and HCl to make the zirconyl
chloride in situ) of suitable concentration and powdered Betaine.
The mixture is stirred at room temperature for a short period of
time and then spray dried to obtain the salt in powder form.
[0039] Method D: An aqueous aluminum chlorohydrate (ACH) solution
made from an activated ACH salt of suitable concentration is mixed
with powdered Betaine. The mixture is stirred at room temperature
to obtain a solution of the salt, or the solution is dried to
remove water to have a powder form of the salt.
[0040] Method E: An aqueous aluminum dichlorohydrate (ADCH)
solution made from an ADCH salt of suitable concentration is mixed
with powdered Betaine. The mixture is stirred at room temperature
to obtain a solution of the salt, or the solution is dried to
remove water to have a powder form of the salt.
[0041] Method F: An aqueous solution made of zirconyl chloride
(ZrOCl.sub.2) of suitable concentration is mixed with powdered
Betaine. The mixture is stirred at room temperature to obtain a
solution of the salt, or the solution is dried to remove water to
have a powder form of the salt.
[0042] Examples of commercial salts that may be used in Method B
include glycine-free salts such as aluminum zirconium
trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum
zirconium pentachlorohydrate, and aluminum zirconium
octachlorohydrate.
[0043] If the product is used as a solid powder, the size of the
particles of antiperspirant active of the invention currently does
not appear to be critical and may include conventional sizes such
as in the range of 2 to 100 microns, with selected grades having an
average particle size of 30-40 microns; finer sized grades having
an average particle size distribution from 2-10 microns with an
average size of about 7 microns as made by a suitable dry-grinding
method; and micronized grades of the type described in a co-pending
patent application U.S. Ser. No. 9/579,322 having an average
particle size of less than or equal to 2 microns, particularly less
than or equal to 1.5 microns.
[0044] The enhanced salts of this invention may be used to
formulate antiperspirants having improved efficacy. Such
antiperspirants include solids such as sticks and creams (creams
sometimes being included in the term "soft solid"), gels, liquids
(such as are suitable for roll-on products), and aerosols. The
forms of these products may be suspensions or emulsions.
[0045] Examples of suitable formulations include the following:
[0046] Sticks--Stick products may be made with conventional gelling
agents such as stearyl alcohol and dibenzylidene sorbitol. A sample
formulation is as follows:
[0047] 40-55% (particularly 45%) cyclomethicone (especially D5
cyclomethicone)
[0048] 20-30% (particularly 21%) stearyl alcohol
[0049] 7-15% (particularly 10%) talc
[0050] 15-22% (particularly 22%) antiperspirant active in powder
form
[0051] 1-3% (particularly 2%) fragrance
[0052] Roll Ons--
[0053] 45-65% (particularly 55%) cyclomethicone (especially D5
cyclomethicone)
[0054] 0.1-10% (particularly 3%) cyclomethicone/dimethicone
copolyol (such as Dow Corning 2-5185 C)
[0055] 10-25% (particularly 20%) antiperspirant active in solution
form (25-45% actives on an anhydrous basis in water)
[0056] 5-30% (particularly 20%) water
[0057] 1-3% (particularly 2%) fragrance
[0058] Soft solids--Soft solids may be made with formulations
described in co-pending patent application (U.S. Ser. No. 9/273,152
and PCT Publication WO 99/51192. A sample formulation is as
follows:
[0059] 40-70% (particularly 50%) elastomer in cyclomethicone
(KSG-15 from Shin-Etsu)
[0060] 5-15% (particularly 6%) polyethylene (for example, beads
having a density in the range of 0.91-0.98 g/cm.sup.3 and an
average particle size in the range of 5-40 microns)
[0061] 10-20% (particularly 15%) C12-15 alkylbenzoate (FINSOLV TN
from Finetex)
[0062] 0.1-25%% (particularly 22%) antiperspirant active in powder
form
[0063] 1-15% (particularly 5%) dimethicone (particularly with a
viscosity of 100 centistokes)
[0064] 1-3% (particularly 2%) fragrance
[0065] Gels--Gels may be made with a variety of formulations such
as
[0066] 5-50% (particularly 29%) cyclomethicone (particularly
D5)
[0067] 0.1-10% (particularly 3%) cyclomethicone/dimethicone
copolyol (such as Dow Corning 2-5185 C)
[0068] 0-10% (particularly 5%) hydrogenated polyisobutene 250
[0069] 0-10% (particularly 5%) C12-15 alkylbenzoate (FINSOLV TN
from Finetex)
[0070] 0-10% (particularly 5%) dimethicone (particularly with a
viscosity of 100 centistokes)
[0071] 0.1-25% (particularly 20%) antiperspirant active in powder
form or 10-25% (particularly 20%) of active in solution (25-45%
actives on an anhydrous basis)
[0072] 5-50% (particularly 30%) water
[0073] 1-3% (particularly 2%) fragrance
[0074] Note that in the explanation of the invention, where water
is listed it is intended to count the contribution of the water
present in the antiperspirant solution as part of the overall water
content. Thus, water is sometimes listed as part of the actives
solution or sometimes listed separately.
[0075] In a preferred embodiment the refractive indices of the
external and internal phases are matched within 0.005 to obtain a
clear product.
[0076] Particular formulations of interest include:
[0077] Formulation A:
[0078] 0.5-2.5% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0079] 55-65% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0080] 1-10% PPG-3 myristyl ether
[0081] 10-25% antiperspirant active of the invention
[0082] 10-25% water
[0083] 0.5-1.5% fragrance
[0084] Formulation B
[0085] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0086] 40-60% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0087] 1-5% cyclomethicone (in addition to that found in the
elastomer)
[0088] 4-12% PPG-3 myristyl ether
[0089] 15-30% antiperspirant active of the invention
[0090] 15-35% water
[0091] 0.5-1.5% fragrance
[0092] Formulation C
[0093] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0094] 1-10% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0095] 40-55% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0096] 3-8% PPG-3 myristyl ether
[0097] 15-20% antiperspirant active of the invention 20-30%
water
[0098] 1.0-3.0% fragrance
[0099] Formulation D
[0100] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0101] 40-60% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0102] 3-8% PPG-3 myristyl ether
[0103] 15-30% antiperspirant active of the invention
[0104] 15-30% water
[0105] 0.5-1.5% fragrance
[0106] 1-10% diethylhexyl naphthalate
[0107] Formulation E
[0108] 0.5-2.5% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0109] 60-70% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0110] 7-10% antiperspirant active of the invention
[0111] 25-35% water
[0112] 1-10% methylpropylene diol (MPDiol)
[0113] 0.5-1.5% fragrance
[0114] Formulation F
[0115] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0116] 6-10% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0117] 35-45% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0118] 6-10% PPG-3 myristyl ether
[0119] 40-50% antiperspirant active of the invention as 43% active
in water
[0120] no additional water
[0121] 0.5-1.0% fragrance
[0122] Formulation G
[0123] 0.1-0.6% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0124] 4-7% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0125] 40-50% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0126] 4-7% PPG-3 myristyl ether
[0127] 40-50% antiperspirant active of the invention as 43% active
in water no additional water
[0128] 0.5-1.0% fragrance
[0129] Formulation H
[0130] 0.5-2.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0131] 1-7% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0132] 40-50% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0133] 45-55% antiperspirant active as 43% active of the invention
in water
[0134] no additional water
[0135] 0.5-1.5% fragrance
[0136] Formulation I
[0137] 2-7% dimethicone copolyol (for example, Dow Corning 2-5185C
(48%))
[0138] 0.1-1% Oleath-20
[0139] 1-5% C12-15 alkyl benzoate (FINSOLV TN)
[0140] 15-25% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0141] 15-25% antiperspirant active
[0142] 15-30% water
[0143] 0.5-1.5% fragrance
[0144] The cosmetic composition according to the present invention
can be packaged in conventional containers, using conventional
techniques. Where a gel, cream or soft-solid cosmetic composition
is produced, the composition can be introduced into a dispensing
package (for example, conventional packages for gels with glide on
applicators, jars where the gel or cream is applied by hand, and
newer style packages having a top surface with pores) as
conventionally done in the art. Thereafter, the product can be
dispensed from the dispensing package as conventionally done in the
art, to deposit the active material, for example, on the skin. For
sticks, sprays, aerosols and roll-ons the compositions can be
placed in a conventional types of container (with the inclusion of
propellants in aerosols). This provides good deposition of the
active material on the skin.
[0145] Compositions of the present invention can be formulated as
clear, translucent or opaque products, although clear products are
preferred. A desired feature of the present invention is that a
clear, or transparent, cosmetic composition, (for example, a clear
or transparent deodorant or antiperspirant composition) can be
provided. The term clear or transparent according to the present
invention is intended to connote its usual dictionary definition;
thus, a clear liquid or gel antiperspirant composition of the
present invention allows ready viewing of objects behind it. By
contrast, a translucent composition, although allowing light to
pass through, causes the light to be scattered so that it will be
impossible to see clearly objects behind the translucent
composition. An opaque composition does not allow light to pass
therethrough. Within the context of the present invention, a gel or
stick is deemed to be transparent or clear if the maximum
transmittance of light of any wavelength in the range 400-800 nm
through a sample 1 cm thick is at least 35%, preferably at least
50%. The gel or liquid is deemed translucent if the maximum
transmittance of such light through the sample is between 2% and
less than 35%. A gel or liquid is deemed opaque if the maximum
transmittance of light is less than 2%. The transmittance can be
measured by placing a sample of the aforementioned thickness into a
light beam of a spectrophotometer whose working range includes the
visible spectrum, such as a Bausch & Lomb Spectronic 88
Spectrophotometer. As to this definition of clear, see European
Patent Application Publication No. 291,334 A2. Thus, according to
the present invention, there are differences between transparent
(clear), translucent and opaque compositions.
EXAMPLES
[0146] The following Examples are offered as illustrative of the
invention and are not to be construed as limitations thereon. In
the Examples and elsewhere in the description of the invention,
chemical symbols and terminology have their usual and customary
meanings. In the Examples as elsewhere in this application values
for n, m, etc. in formulas, molecular weights and degree of
ethoxylation or propoxylation are averages. Temperatures are in
degrees C. unless otherwise indicated. If alcohol is used, it is
95% unless otherwise indicated. Unless otherwise indicated, "water"
or "DI water" mean deionized water. As is true throughout the
application, the amounts of the components are in weight percents
based on the standard described; if no other standard is described
then the total weight of the composition is to be inferred. Various
names of chemical components include those listed in the CTFA
International Cosmetic Ingredient Dictionary (Cosmetics, Toiletry
and Fragrance Association, Inc., 7.sup.th ed. 1997). While specific
amounts of particular elastomers have been described, there are
chemical differences in the variety of elastomers that are
available. The use of different elastomers may result in the need
to increase or decrease the amount of elastomer used in a
particular formulation, especially if a clear product is
desired.
[0147] In the Examples, as elsewhere in the description of the
invention, the reference is made to using the antiperspirant active
either as a powder or in some type of solution such as dissolved in
water at a concentration of 25-45% actives on an anhydrous
basis.
[0148] In the Examples, the Betaine used is the Betaine of Formula
I.
Examples
Antiperspirant Salts
Example 1
[0149] A salt solution may be made by dissolving 19.26 g
ZrOCl.sub.2.8H.sub.2O in 49.6 g of water and then adding 8.39 g
Betaine anhydrous. After everything is dissolved, an ACH powder
(22.65 g of Chlorhydrol from Reheis Chemical Co., Berkeley Heights,
N.J.) into the solution with additional DI water so that the total
weight of the solution is 100 g. The solution is shaken or stirred
to make sure the solution is clear. Optionally, the solution can be
spray dried or freeze-dried to make a powder sample. This 30% salt
solution (anhydrous basis) has the following composition:
1 Al/Zr = 3.5 Metal/Cl = 1.2 Betaine/Zr = 1.2 Al: 5.64% 0.00209
Mole Zr: 5.45% 0.000597 Mole Cl: 7.95% 0.00224 Mole Betaine 8.39%
0.000716 Mole
Example 2
[0150] A salt may solution be made by dissolving 19.26 g
ZrOCl.sub.2.8H.sub.2O in 49.6 g of water and then adding 5.36 g
Betaine anhydrous. After everything is dissolved, an ACH powder
(22.65 g of Chlorhydrol from Reheis) into the solution with
additional DI water so that the total weight of the solution is 100
g. The solution is shaken or stirred to make sure the solution is
clear. Optionally, the solution can be spray dried or freeze-dried
to make a powder sample. This 30% salt solution (anhydrous basis)
has the following composition:
2 Al/Zr = 3.5 Metal/Cl = 1.2 Betaine/Zr = 0.76 Al: 5.64% 0.00209
Mole Zr: 5.45% 0.000597 Mole Cl: 7.95% 0.00224 Mole Betaine 5.36%
0.000457 Mole
Example 3
[0151] A salt solution may be made by dissolving e 19.26 g of
ZrOCl.sub.2.8H.sub.2O in 40 gm of distilled water and then adding
9.68 g of Betaine monohydrate. After everything is dissolved, an
ACH powder (22.65 g of Chlorhydrol from Reheis) is added to the
solution with additional DI water so that the total weight of the
solution is 100 g. The solution is shaken or stirred to make sure a
clear solution of 30% salt solution (anhydrous basis) is obtained.
This 30% salt solution (anhydrous basis) has the following
composition:
3 Al/Zr = 3.5 M/Cl = 1.2 Btn/Zr = 1.2 Al: 5.64% 0.00209 Mole Zr:
5.45% 0.000597 Mole Cl: 7.95% 0.00224 Mole Betaine 8.39% 0.000716
Mole
[0152] The solution can be spray dried or freeze-dried to make a
powder sample if needed.
Example 4
[0153] A salt solution may be made by dissolve 240 g of
ZrOCl.sub.2.8H.sub.2O in 463 g of distilled water and then adding
100.4 g of Betaine monohydrate. After every thing is dissolved, ACH
is added (210 g of ACH Chlorhydrol Powder from Reheis) to the
solution. The solution is shaken or stirred to make sure a clear
solution of 24% (anhydrous) is obtained. This 24% salt solution
(anhydrous basis) has the following composition:
4 Al/Zr = 2.6 Metal/Cl = 1.1 Betaine/Zr = 1.0 Al: 2.7% Zr: 6.9% Cl:
6.85% Betaine 8.86%
[0154] The solution can be spray dried or freeze-dried to make a
powder sample if needed.
Example 5
[0155] A salt solution may be made by mixing 278 g of zirconium
hydroxychloride trihydrate solution (15% Zr and 6.66% Cl) with 76 g
of Betaine monohydrate at room temperature. After everything is
dissolved, ACH is added (400 g of Chlorhydrol Powder solution,
which contains 12.3% of Al and 10.0% of Cl) to the solution. The
combined solution is shaken or stirred to mix the two solutions
well. The final solution then is spray dried or freeze-dried to
make a powder sample.
[0156] The final powder has the following values:
5 Al/Zr = 3.4 Metal/Cl = 1.4 Betaine/Zr = 1.2 Al: 14.2% Zr: 14.5%
Cl: 17.2% Betaine 22.6%
Example 6
[0157] Betaine monohydrate powder (286 g) is added to a zirconium
compound (1000 g of a 31% solution of zirconium oxychloride
(ZrOCl.sub.2)) with stirring. Aluminum chlorohydrate ("ACH") (1120
g of a 50% aqueous ACH solution) is then added with additional
stirring. The final solution is then diluted with distilled water
into an anhydrous concentration of 33.0%, with a Betaine/zirconium
molar ratio of 1.45:1; an aluminum/zirconium molar ratio of 3.56:1,
and a metal/chloride ratio of 1.01:1.
Example 7
[0158] Betaine monohydrate (287 g) is added to a zirconium compound
(1000 g of a 31% solution of zirconium oxychloride (ZrOCl.sub.2)
with stirring. ACH (1204 g of a 50% aqueous ACH solution) is then
added with additional stirring. The final solution is then diluted
with distilled water into an anhydrous concentration of 30.0% with
a Betaine/zirconium molar ratio as 1.45:1; an aluminum/zirconium
molar ratio of 3.82:1, and a metal/chloride ratio of 0.98.
Example 8
[0159] Betaine monohydrate powder (287 g) is added to a zirconium
compound (1000 g of a 31% solution of zirconium oxychloride
(ZrOCl.sub.2)) with stirring. Aluminum chlorohydrate ("ACH") (2800
g of a 20% ACH solution made from a powder (REACH 101, from Reheis,
Berkeley Height, N.J.) is then added with additional stirring. The
final solution is then quickly spray dried to remove water. The
Zirconium/Aluminum/Betaine ("ZAB") powder obtained has a
Betaine/zirconium molar ratio of 1.42:1; an aluminum:zirconium
molar ratio of 3.56:1; and a metal:chloride ratio of 1.05:1.
Example 9
[0160] A solution of aluminum pentachlorohydrex (Reheis Penta-solv,
glycine-free) is prepared by dissolution of 30 g Penta-solv in 62 g
of DI water. After the solution is mixed and becomes clear, 8 gm of
anhydrous Betaine are added and the solution is mixed at room
temperature until clear. The final solution has a Betaine/zirconium
molar ratio of 2.83:1; an aluminum/zirconium molar ratio of 9.56:1,
and a metal/chloride ratio of 1.67:1.
Example 10
[0161] A solution of aluminum octachlorohydrex (Reheis Octa-solv,
glycine-free) is prepared by dissolution of 30 g Octa-solv in 62 g
of DI water. After the solution is mixed and becomes clear, 8 gm of
anhydrous Betaine are added and the solution is mixed at room
temperature until clear. The final solution has a Betaine/zirconium
molar ratio of 2.65:1; an aluminum/zirconium molar ratio of 8.18:1,
and a metal/chloride ratio of 1.40:1.
Example 11
[0162] A solution of aluminum chlorohydrex (ACH, Reheis
Chlorhydrol, 50%) is prepared by dissolution of 30 g ACH in 62 g of
DI water. After the solution is stirred and becomes clear, 8 gm of
anhydrous Betaine are added and the solution is mixed at room
temperature until clear. The final solution has a Betaine/aluminum
molar ratio of 0.25 and an aluminum/chloride ratio of 2.0:1.
Example 12
[0163] A solution of aluminum dichlorohydrex (ADCH, Westchlor 100,
38%) is prepared by dissolution of 30 g ADCH in 62 g of DI water.
After the solution is mixed and becomes clear, 8 g of anhydrous
Betaine is added and the solution is mixed at room temperature
until clear. The final solution has a Betaine/aluminum molar ratio
of 0.61 and an aluminum/chloride ratio of 1.00.
Example 13
[0164] A solution of aluminum chloride hydrate (AlCl.sub.3) is
prepared by dissolution of 30 g AlCl.sub.3 in 62 g of DI water.
After the solution is mixed and becomes clear, 8 gm of anhydrous
Betaine are added and the solution is mixed at room temperature
until clear. The final solution has a Betaine/aluminum molar ratio
of 0.30 and an aluminum/chloride ratio of 0.33.
Example 14
[0165] A 31% solution of zirconium oxychloride (ZrOCl.sub.2) is
mixed with 8 g anhydrous Betaine and stirred at room temperature
until clear. The final solution has a Betaine/zirconium molar ratio
of 0.43 and a zirconium/chloride ratio of 0.50.
Analytical Data for Examples 1, 2 and 10
[0166] Size exclusion chromatography ("SEC") or gel permeation
chromatography ("GPC") are methods frequently used for obtaining
information on polymer distribution in antiperspirant salt
solutions. With appropriate chromatographic columns, at least five
distinctive groups of polymer species can be detected in a ZAG,
appealing in a chromatogram as peaks 1, 2, 3, 4 and a peak known as
"5,6". Peak 1 is the larger Zr species (greater than 60 Angstroms).
Peaks 2 and 3 are larger aluminum species. Peak 4 is the smaller
aluminum species (aluminum oligomers) and has been correlated with
enhanced efficacy for both ACH and ZAG salts. Peak 5,6 is the
smallest aluminum species. The relative retention time ("Kd") for
each of these peaks varies depending on the experimental
conditions. This method is also applicable to ZAB salts. Data for
Table A was obtained using the SEC method described in an issued
patent owned by the same company as a this case, U.S. Pat. No.
6,066,314, incorporate by reference as to the test method described
therein.
6TABLE 1 SEC Polymer distribution of the ZAB sample 1 from Example
1 at room temperature. Time (days) Peak1/All Peaks 8 0.003 15 0.008
31 0.001 70 0.039 86 0.070 122 0.086 146 0.152 192 0.206 294
0.163
[0167]
7TABLE 2 SEC Polymer distribution of the ZAB sample 1 from Example
1 at 40 degree C. Time (days) Peak1/All Peaks 8 0.027 15 0.070 31
0.121 70 0.148 86 0.144 129 0.185 146 0.168
[0168]
8TABLE 3 SEC Polymer distribution of the ZAB sample 1 from Example
2 at room temperature. Time (days) Peak1/All Peaks 8 0.098 15 0.146
31 0.196 70 0.227 86 0.251 122 0.283 146 0.315 192 0.400 294
0.363
[0169]
9TABLE 4 SEC Polymer distribution of the ZAB sample 1 from Example
2 at 40 degree C. Time (days) Peak1/All Peaks 8 0.270 15 0.260 31
0.311 70 0.307 86 0.342 129 0.365 146 0.349
[0170]
10TABLE 5 SEC Polymer distribution of the ZAB sample 1 from Example
10 at room temperature. Time (days) Peak1/All Peaks 4 0.214 24
0.199 45 0.191 80 0.193 108 0.190
Example 15
General Method for Making Antiperspirant Products
[0171] In general, the external and internal phases are formed
separately either at room temperature or with heating as described
below. The internal phase is added to the external phase very
slowly while stirring at to form an emulsion. After the addition
has been completed, the mixture is stirred at higher speed to
achieve a homogeneous mixture. The final formula viscosity is then
achieved by homogenizing the emulsion under either batch or
continuous process conditions as described below. The fragrance may
be added at any time during the process prior to final
homogenization.
[0172] Preparation of the External Phase:
[0173] The ingredients to be used in the external phase (including
the elastomer) are weighed out at room temperature and combined in
a suitable vessel such as a 2 liter glass beaker. The mixture is
stirred at about 500 rpm for 15-20 minutes using an overhead mixer
such as a Lightnin' Mixer Model L1003. If a waxy or solid emollient
is to be added to the external (also called "continuous") phase,
the mixture may be heated to facilitate dissolution while stirring
then cooled to room temperature prior to combination with the
internal phase as described below. If an elastomer component used
it is obtained as a suspension of elastomer in cyclomethicone (for
example at a concentration of 6% active in D5 cyclomethicone). The
elastomer component is added to the external phase with stirring at
high speed (500-700 rpm for a 0.5 kilogram batch) until no
particles of elastomer are visible to the eye.
[0174] Preparation of the Internal Phase:
[0175] The internal dispersed phase is prepared as described below.
Ingredients are mixed for a time sufficient to achieve homogeneity.
The antiperspirant active used is weighed into a large beaker
equipped with an overhead stirrer. Other internal phase ingredients
are then added while stirring.
[0176] The fragrance (if any is used) is added last and may be
added either to the internal phase or the external phase or the
final formula prior to homogenization. For many of the examples
described here, one could add the fragrance to the internal
phase.
[0177] If an optional non-ionic emulsifier such as Oleath-20 is
used, the emulsifier and propylene glycol are combined in a
separate beaker and heated to 40 degrees C. with stirring until the
non-ionic emulsifier completely dissolved. The heat is turned off
and the remaining ingredients to be used in the internal phase,
including the antiperspirant active are weighed out and added to
the mixture of propylene glycol and non-ionic emulsifier.
[0178] If water or a salt solution is used, the internal phase is
prepared as follows. The solution containing antiperspirant active
salt as received from supplier is weighed into a large beaker
equipped with a magnetic stirrer. Additional ingredients such as
propylene glycol, ethanol and water are added while stirring. If a
salt water solution is used (such as for NaCl, etc.), the salt
water solution is prepared by dissolving the crystalline salt in
water in a separate beaker and stirring until dissolved. The salt
water solution is then added to the rest of the internal phase and
the mixture is stirred until homogeneous.
[0179] Preparation of the Emulsion:
[0180] The internal phase made as described above is then added to
the external phase over the course of 15-30 minutes while stirring
at a speed of 500-700 rpm. After the addition is complete, the
mixture is stirred at 500-700 rpm for 20 minutes using a Lightnin
Mixer Model L1003. The mixture is then homogenized for 2-4 minutes
(especially 3 minutes) using a homogenizer from Greerco Corp.,
Hudson, N.H. at a reading of about 60 on a Powerstat Variable
Autotransformer from Superior Electric Co., Bristol, Conn.
[0181] Further Processing:
[0182] The product is then further processed by homogenization to
achieve the desired final viscosity. This can be done by using a
Gilford-Wood Model 1-L (Greerco Corp., Hudson, N.H.) homogenizer.
The homogenizer speed is controlled by a Powerstat Variable
Autotransformer Type 3PN116B (Superior Electronic. Co., Bristol,
Conn.). Typical voltage setting and processing time are chosen to
give a desired final formula viscosity.
[0183] An other method of homogenization of the final product is to
pass the emulsion through a colloid mill such as a Sonic Tri-Homo
Colloid Mill or a process sonolator such Sonic Production Sonolator
200-30 both available from Sonic Corporation of Stratford, Conn.
Process conditions are chosen to give the desired final product
viscosity.
Examples 16-36
Compositions Based on Example 15
[0184] The methods described in Example 15 may be used to make the
products listed in Tables 6 and 7 with the types and amounts of
ingredients listed in the Tables 6 and 7. Amounts are in percent by
weight based on the total weight of the composition.
11TABLE 6 Ingredient Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex.
22 Ex. 23 Ex. 24 Ex. 25 External Phase Elastomer (KSG-15, 6% 62 50
48 40 41.5 42.0 46.5 35 32.17 25 active) Dimethicone copolyol 2 2
1.5 4 1.5 0.5 1.0 1.0 2.48 1.0 (Dow Corning 2-5185, 48% active in
cyclomethicone) Hydrogenated 0 0 5 8 5 5 5 5 4.95 0 polyisobutene
(Polyiso 250) PPG-3 Myristyl Ether 5 5 4.5 0 4.5 5.0 0 0 0 5 C12-15
alkyl benzoate -- -- -- 2.0 -- -- -- -- -- -- (FINSOLV TN)
Cyclomethicone (Dow 0 2 0 0 0 0 0 0 0 0 Corning 245) Fragrance 1 1
1 1 1 1 1 1 1 0 Internal Phase Antiperspirant Active.sup.a 15 20
17.5 19.5 46.5 46.5 46.5 58 59.40 48.45 Water (deionized).sup.b 15
20 22.5 25 0 0 0 0 0 0 Oleath-20 (HLB > 8) 0 0 0 0.5 0 0 0 0 0
19.55 Total 100 100 100 100 100 100 100 100 100 100 .sup.a= Any of
the actives described in Examples 1-14 may be used. .sup.b= Note
that in the examples, sometimes the antiperspirant active is listed
as a solution (which will include a water component) under the
"active" designation with little or no water and sometimes the
active and water are listed separately.
[0185]
12TABLE 7 Ingredient Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 Ex.
32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 External Phase Elastomer (DC 9040)
12% 55 62 62 40 41.5 25 31.5 21 17 17 50 active) Dimethicone
copolyol 1 2 2 4 1 1 2.5 1 1 1 2 (Dow Corning 2-5185, 48% active in
cyclomethicone) Hydrogenated 5 -- -- 8 5 -- 5 1.5 1.5 1.5 --
polyisobutene (Polyiso 250) PPG-3 Myristyl Ether 3 4.5 5 -- 5 5 --
0.5 0.5 0.5 5.0 C12-15 alkyl benzoate -- -- -- 2 -- -- -- -- -- --
-- (FINSOLV TN) Cyclomethicone (Dow -- -- -- -- -- -- -- 5 9.0 9.0
2.0 Corning 245) Fragrance 1 1 1 1 1 1 1 1 1 1 1 Internal Phase
Antiperspirant Active.sup.a 15 15.5 30 19.5 46.5 48.45 60.0 60.5
63.68 60.13 20 Water (deionized).sup.b 20 15 -- 25 -- 19.55 -- 9.5
6.32 9.87 20 Oleath-20 (HLB > 8) -- -- -- 0.5 -- -- -- -- -- --
-- Total 100 100 100 100 100 100 100 100 100 100 100 .sup.a= See
explanation of actives used. Actives according to Examples 1-14 may
be used. .sup.b= Note that in the examples, sometimes the
antiperspirant active is listed as a solution (which will include a
water component) under the "active" designation with little or no
water and sometimes the active and water are listed separately.
* * * * *